EP3155056B1 - Ink, ink cartridge, inkjet recording apparatus, printed matter, photopolymerizable compound, photocurable composition, three-dimensional object formation material, and three-dimensional object - Google Patents

Ink, ink cartridge, inkjet recording apparatus, printed matter, photopolymerizable compound, photocurable composition, three-dimensional object formation material, and three-dimensional object Download PDF

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Publication number
EP3155056B1
EP3155056B1 EP15807470.8A EP15807470A EP3155056B1 EP 3155056 B1 EP3155056 B1 EP 3155056B1 EP 15807470 A EP15807470 A EP 15807470A EP 3155056 B1 EP3155056 B1 EP 3155056B1
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Prior art keywords
ink
group
compound
examples
dye
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EP15807470.8A
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German (de)
English (en)
French (fr)
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EP3155056A4 (en
EP3155056A1 (en
Inventor
Mitsunobu Morita
Soh Noguchi
Daisuke Miki
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority claimed from PCT/JP2015/002502 external-priority patent/WO2015190037A1/en
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Publication of EP3155056A1 publication Critical patent/EP3155056A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/17—Ink jet characterised by ink handling
    • B41J2/175—Ink supply systems ; Circuit parts therefor
    • B41J2/17503—Ink cartridges
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present invention relates to an inkjet recording apparatus.
  • An inkjet recording method is known as a method for forming an image over a recording medium such as paper.
  • This recording method has a high ink consumption efficiency, is excellent in resource saving, and can save ink costs per unit recording operation low.
  • PTL 1 discloses a (meth)acrylate compound having a specific urethane structure, and an active energy ray-curable composition containing the compound, and an inkjet recording ink composition.
  • PTLs 2 and 3 disclose an active energy ray-curable composition containing a (meth)acrylate compound of which mother nucleus is alkoxy group-modified hydrocarbon, and an inkjet recording ink composition.
  • PTL 4 discloses a dental adhesive agent composition containing a glycerin di(meth)acrylate compound.
  • PTL 5 discloses a side chain type polymerizable compound having an ether structure (-O-) or an ester structure (-COO-) on both of a main chain and a side chain of a molecule thereof, and a liquid crystal device using the same.
  • ether structure -O-
  • -COO- ester structure
  • An object of the present invention is to provide an inkjet recording apparatus that uses a photopolymerizable compound having a lower viscosity and less odor than conventional ones, and is excellent in photopolymerizability and photocurability.
  • the present invention can provide an inkjet recording apparatus that uses a photopolymerizable compound having a lower viscosity and less odor than conventional ones, and is excellent in photopolymerizability and photocurability.
  • a compound represented by general formula (1) below that is contained in an ink of the present invention contains: two (meth)acrylic acid ester structures as polymerizable functional groups; and one group having an ester structure as a branch structure.
  • R 1 represents a hydrogen atom or a methyl group
  • n represents an integer of 2
  • X represents Y represents a group having an ester structure represented by general formula (2) below, or general formula (3) below
  • R 2 represents a hydrocarbon group having 1 to 10 carbon atoms selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, which may be straight-chained or branched
  • m represents an integer of 1.
  • the compound containing a plurality of (meth)acrylic acid ester structures, which are polymerizable functional groups, in a molecule thereof can form a cross-linked structure between the molecules thereof upon a polymerization reaction, and can be improved in curability.
  • the molecular weight and viscosity of the compound will increase, as the number of (meth)acrylic acid ester structures in a molecule thereof increases, although curability thereof will be improved.
  • n in the general formula (1) above is 2.
  • incorporation of a polar structure in the molecules of a photopolymerizable compound will enhance interactions between the molecules of the monomer and bring polymerizable functional groups thereof close to each other to thereby enhance polymerization reactivity of the monomer.
  • incorporation of a primary or secondary hydroxyl group (-OH) or a protic polar structure such as an amino group (-NH 2 ) in a monomer will increase the viscosity of the monomer, and cause troubles or limitations during use of the monomer as a photopolymerizable composition for various types of inks, etc.
  • the viscosity of a monomer increases, the mobility of the molecules of the monomer declines, which may inhibit the progress of a polymerization reaction of the monomer.
  • incorporation of an aprotic polar structure in a monomer will result in lower intermolecular interactions than by incorporation of a protic polar structure as above, and will enable simultaneous satisfaction of suppression of viscosity thickening and enhancement of photopolymerization reactivity and photocurability.
  • incorporation of a group having an ester structure is considered to suppress viscosity thickening based on adequate flexibility of its linking portion linking to the mother nucleus structure and adequate intensity of the polarity of the ester structure, and enable simultaneous satisfaction of enhancement of photopolymerization reactivity and photocurability owing to the intermolecular interactions and viscosity suppression.
  • incorporation of an ether structure which is an aprotic polar structure likewise, is considered to be less capable of enhancing photopolymerization reactivity and photocurability of a monomer, because of resulting too low intermolecular interactions and a great freedom of the ether structure.
  • incorporation of a urethane structure as an aprotic polar structure is considered to increase the viscosity of a monomer because of a stronger polar structure of the urethane structure than the ester structure, and stiffness of the urethane structure portion.
  • ester structure which however is bonded reversely from the present invention (i.e., branched via a carbonyl carbon, not an oxygen atom), will incur viscosity thickening of a monomer, because such bonding deprives the ester bond portion of its freedom, leading to stiffness of the molecules.
  • the compound represented by the general formula (1) above is excellent in photopolymerizability and photocurability because intermolecular interactions and a degree of molecular freedom thereof can be adjusted to a fine balance, and has less odor. Furthermore, the compound can be suppressed from viscosity thickening, and will have a low viscosity particularly when the polar group thereof is a group having an ester structure. Hence, the compound represented by the general formula (1) above is suitable for an ink.
  • Y represents a group having an ester structure.
  • R 2 is a hydrocarbon group having 1 to 10 carbon atoms, selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. These groups may be straight-chained, or may be branched. Among these, a methyl group, and an ethyl group are preferable.
  • the photopolymerizable compound of the present invention may be a mixture of two or more different compounds.
  • examples of the different compounds include structural isomers.
  • the mixing ratio is not particularly limited.
  • a preferable range of the viscosity of the photopolymerizable compound of the present invention is different depending on the applications of the ink. Besides, there may be cases when a plurality of photopolymerizable compounds are used in combination. Therefore, a preferable viscosity range cannot be determined flatly.
  • the viscosity thereof at 25°C is 50 mPa • s or lower, preferably 20 mPa • s or lower, and more preferably 15 mPa • s or lower.
  • the content of the photopolymerizable compound in the ink is typically from 20% by mass to 98% by mass, preferably from 30% by mass to 90% by mass, and more preferably from 30% by mass to 80% by mass.
  • the ink further contain a photopolymerization initiator.
  • the photopolymerization initiator examples include a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), and a photoanionic polymerization initiator (photobase generator). Two or more kinds may be used in combination. Among these, a photoradical polymerization initiator and a photoanionic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
  • a photopolymerization initiator is a compound that generates polymerization initiator species by absorbing an active energy ray.
  • An active energy ray is not particularly limited, and examples thereof include a ⁇ ray, a ⁇ ray, an electron beam, an ultraviolet ray, visible light, and an infrared ray.
  • the photoradical polymerization initiator is not particularly limited, and examples thereof include aromatic ketones, an acyl phosphine oxide compound, an aromatic onium salt compound, an organic peroxide, a thio compound, a hexaaryl biimidazole compound, a ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, and an alkyl amine compound.
  • photoradical polymerization initiator examples include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethyl thioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-4'-isopropyl propiophenone, 1-hydroxycyclohexyl phenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1-one, ethyl 2-benzyl-2-dimethylamin
  • a mass ratio of the photopolymerization initiator relative to a total amount of the photopolymerizable compound and a colorant is typically from 0.01 to 0.50, preferably from 0.02 to 0.40, and more preferably from 0.05 to 0.30.
  • the ink may further contain a colorant, and can hence form a color image.
  • the colorant is not particularly limited, and examples thereof include a pigment, an oil-soluble dye, a water-soluble dye, and a dispersive dye. Two or more kinds may be used in combination. Among these, a pigment and an oil-soluble dye are preferable because they have an excellent weatherability and a rich color reproducibility, and a pigment is more preferable.
  • the colorant be a compound that does not function as a polymerization inhibitor, in order not to reduce sensitivity to an active energy ray for a photopolymerization reaction.
  • red pigment or a magenta pigment examples include: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, and 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; and Pigment Orange 13, 16, 20, and 36.
  • Examples of a blue pigment or a cyan pigment as the pigment include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60.
  • Examples of a green pigment as the pigment include Pigment Green 7, 26, 36, and 50.
  • Examples of a yellow pigment as the pigment include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, and 193.
  • Examples of a black pigment as the pigment include Pigment Black 7, 28, and 26.
  • Examples of a white pigment as the pigment include Pigment White 6, 18, and 21.
  • Examples of a yellow oil-soluble dye include: an aryl or heteryl azo dye having phenol, naphthol, aniline, pyrazolone, pyrrolidone, or an open-chain active methylene compound as a coupling component; a methine dye having an open-chain active methylene compound as a coupling component, such as an azomethine dye, a benzylidene dye, and a monomethine oxonol dye; a quinone-based dye such as a naphthoquinone dye, and an anthraquinone dye; a quinophthalone dye; a nitro-nitroso dye; an acridine dye; and an acridinone dye.
  • an aryl or heteryl azo dye having phenol, naphthol, aniline, pyrazolone, pyrrolidone, or an open-chain active methylene compound as a coupling component such as an azomethin
  • magenta oil-soluble dye examples include: an aryl or heteryl azo dye having phenol, naphthol, or aniline as a coupling component; a methine dye having pyrazolone or a pyrazolotriazole as a coupling component, such as an azomethine dye, an arylidene dye, a styryl dye, a merocyanine dye, and an oxonol dye; a carbonium dye such as a diphenylmethane dye, a triphenylmethane dye, and a xanthene dye; a quinone dye such as naphthoquinone, anthraquinone, and anthrapyridone; and a condensed polycyclic dye such as dioxazine.
  • Examples of a cyan oil-soluble dye include: an indoaniline dye; an indophenol dye; a polymethine dye having pyrrolotriazole as a coupling component, such as an azomethine dye, a cyanine dye, an oxonol dye, and a merocyanine dye; a carbonium dye such as a diphenylmethane dye, a triphenylmethane dye, and xanthene dye; a phthalocyanine dye; an anthraquinone dye; an aryl or heteryl azo dye having phenol, naphthol, or aniline as a coupling agent; and an indigo or thioindigo dye.
  • an indoaniline dye such as an azomethine dye, a cyanine dye, an oxonol dye, and a merocyanine dye
  • a carbonium dye such as a diphenylmethane dye, a triphen
  • oil-soluble dye examples include: C.I. solvent black 3, 7, 27, 29, and 34; C.I. solvent yellow 14, 16, 19, 29, 30, 56, 82, 93, and 162; C.I. solvent red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132, and 218; C.I. solvent violet 3; C.I. solvent blue 2, 11, 25, 35, 38, 67, and 70: C.I. solvent green 3, and 7; and C.I. solvent orange 2.
  • dispersive dye examples include: disperse yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184:1, 186, 198, 199, 201, 204, 224, and 237; C.I. disperse orange 13, 29, 31:1, 33, 49, 54, 55, 66, 73, 118, 119, and 163; C.I.
  • the pigment be dispersed adequately in the ink.
  • a disperser for dispersing the pigment is not particularly limited, and examples thereof include a ball mill, a sand mill, a ring mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker.
  • a dispersant may be added for dispersing the pigment.
  • the dispersant is not particularly limited, but a polymeric dispersant is preferable.
  • a mass ratio of the dispersant relative to the pigment is typically from 0.01 to 0.50.
  • An average particle diameter of the pigment in the ink is typically from 0.005 ⁇ m to 0.5 ⁇ m, preferably from 0.01 ⁇ m to 0.45 ⁇ m, and more preferably from 0.015 ⁇ m to 0.4 ⁇ m. This makes it possible to suppress clogging of head nozzles, and maintain storage stability, transparency, and photocurability of the ink.
  • the content of the colorant in the ink is typically from 0.5% by mass to 10% by mass, and preferably from 1% by mass to 8% by mass.
  • the content of the colorant in a white ink that contains a white pigment such as titanium oxide as the colorant is typically from 5% by mass to 30% by mass, and preferably from 10% by mass to 25% by mass. This makes it possible to ensure a hiding power.
  • the ink may contain any other photopolymerizable compound than the compound represented by the general formula (1).
  • a mass ratio of the any other photopolymerizable compound relative to the compound represented by the general formula (1) is typically from 0.01 to 100, and preferably from 0.1 to 50.
  • the any other photopolymerizable compound is not particularly limited, and examples thereof include a photoradically polymerizable compound, a photocationically polymerizable compound, and a photoanionically polymerizable compound. Two or more kinds may be used in combination.
  • the photoradically polymerizable compound is not particularly limited except that it should be a compound having one or more photoradically polymerizable ethylenic unsaturated groups, and encompasses a monomer, an oligomer, a polymer, etc.
  • examples thereof include: unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, salts thereof, and compounds derived from these; an anhydride having an ethylenic unsaturated group; acrylonitrile; styrene; unsaturated polyester; unsaturated polyether; unsaturated polyamide; and unsaturated urethane.
  • the photoradically polymerizable compound include: acrylic acid derivatives such as 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate
  • combination of the photopolymerizable compound and the photopolymerization initiator include a combination of a photocationically polymerizable compound and a photocationic polymerization initiator, and a combination of a photoanionically polymerizable compound and a photoanionic polymerization initiator, in addition to a combination of a photoradically polymerizable compound and a photoradical polymerization initiator.
  • the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound.
  • Examples of the photocationic polymerization initiator include: B(C 6 F 5 ) 4 , PF 6 - , AsF 6 - , SbF 6 - , and CF 3 SO 3 - salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium; a sulfonated product that can generate a sulfonic acid; a halide that can generate hydrogen halide; and an iron allene complex.
  • Examples of the photoanionically polymerizable compound include an epoxy compound, a lactone compound, an acrylic compound, and a methacrylic compound. Among these, acrylic-based compounds and methacrylic-based compounds presented as examples of the photoradically polymerizable compound are preferable.
  • photoanionic polymerization initiator examples include an o-nitrobenzyl carbamate derivative, an o-acyl oxyl derivative, and an o-carbamoyl oxime amidine derivative.
  • the ink may further contain a sensitizer in order to promote decomposition of the photopolymerization initiator by active energy ray irradiation.
  • a sensitizer absorbs an active energy ray and becomes an electron-excited state, and contacts the polymerization initiator in this state to thereby promote a chemical change (decomposition, or generation of a radical, an acid, or a base) of the polymerization initiator by such effects as electron migration, energy transfer, heat generation, etc.
  • a mass ratio of the sensitizer relative to the photopolymerization initiator is typically from 5 ⁇ 10 -3 to 200, and preferably from 0.02 to 50.
  • the sensitizer is not particularly limited, and a sensitizing dye that has an absorption wavelength in a wavelength range of from 350 nm to 450 nm.
  • a sensitizing dye that has an absorption wavelength in a wavelength range of from 350 nm to 450 nm.
  • examples thereof include: polynuclear aromatics (e.g., pyrene, perylene, and triphenylene); xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, and rose Bengal); cyanines (e.g., thiacarbocyanine, and oxacarbocyanine); merocyanines (e.g., merocyanine, and carbomerocyanine); thiazines (e.g., thionine, methylene blue, and toluidine blue); acridines (e.g., acridine orange, chloroflavin, and a
  • the ink may further contain a cosensitizer.
  • a consensitizer serves to further enhance the sensitivity of the sensitizing dye to an active energy ray, and suppress polymerization inhibition of the photopolymerizable compound due to oxygen.
  • the cosensitizer is not particularly limited, and examples thereof include: amine-based compounds such as triethanol amine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethyl aniline, and p-methylthiodimethyl aniline; thiol such as 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-4(3H)-quinazoline, and ⁇ -mercaptonaphthalene; and sulfides.
  • amine-based compounds such as triethanol amine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethyl aniline, and p-methylthiodimethyl aniline
  • thiol such as 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-4(3H
  • the ink may further contain a polymerization initiator.
  • a polymerization initiator is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and a cupferron complex of aluminium.
  • the content of the polymerization initiator in the ink is typically from 200 ppm to 20,000 ppm.
  • the viscosity of the ink is typically from 7 mPa • s to 30 mPa • s, and preferably from 7 mPa • s to 25 mPa • s in view of jettability from an inkjet recording apparatus.
  • the ink be free from a solvent because it is an active energy ray-curable ink.
  • the ink may contain a solvent, as long as the curing speed, etc. of the ink are not influenced.
  • the solvent is not particularly limited, and examples thereof include an organic solvent, and water.
  • the content of the organic solvent in the ink is typically from 0.1% by mass to 5% by mass, and more preferably from 0.1% by mass to 3% by mass.
  • the ink may further contain a surfactant, a leveling additive, a matting agent, and a polyester-based resin, a polyurethane-based resin, a vinyl-based resin, an acrylic-based resin a rubber-based resin, or a wax for adjusting film properties.
  • the ink may further contain a stickiness imparting agent (tackifier) free of a polymerization inhibiting property, in order to enhance adhesiveness with polyolefin, PET, etc.
  • tackifier a stickiness imparting agent free of a polymerization inhibiting property
  • the ink may be contained in a container, and can be used in the form of an ink cartridge.
  • the container is not particularly limited, and examples thereof include an ink bag made of an air-impermeable aluminium laminate film or resin film.
  • Fig. 1 shows an example of an ink cartridge.
  • An ink bag 11 has an ink injection port 12 and an ink discharge port 13.
  • the ink bag 11 is filled with an ink through the ink injection port 12, deaerated of residual air in the ink bag 11, and then hermetically sealed with the ink injection port 12 fusion-bonded.
  • the ink discharge port 13 is pierced with a needle provided on the body of an inkjet recording apparatus, and the ink is supplied into the inkjet recording apparatus.
  • the ink discharge port 13 is made of a rubber material.
  • the ink bag 11 is contained in a cartridge case 14 made of plastic, and detachably attached into the inkjet recording apparatus in the form of an ink cartridge 10.
  • the detachable configuration makes it possible to improve work efficiency of ink replenishment, replacement, etc.
  • An inkjet recording apparatus includes an ink cartridge, and a jet head configured to perform recording by jetting an ink.
  • a method for jetting an ink is not particularly limited, and examples thereof include a serial jetting method, and an on-demand method.
  • Examples of the on-demand method include a piezo method, a thermal method, and an electrostatic method.
  • a printing mechanism of the inkjet recording apparatus will be described with reference to Fig. 2 .
  • the reference numerals 23 denote printing units.
  • the printing units 23a, 23b, 23c, and 23d for yellow, magenta, cyan, and black respectively jet inks onto a print target base material 22 fed from a print target base material feeding roll 21. Yellow, magenta, cyan, and black inks are jetted separately. After this, the inks are irradiated and cured with ultraviolet rays from light sources 24a, 24b, 24c, and 24d for photo-curing the inks, to thereby form a color image. After this, the print target base material 22 is conveyed to a process unit 25 and a printed matter take-up roll 26.
  • the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism in order for the inks to be liquefied at the ink jetting portions.
  • a contact or contactless mechanism for cooling the base material to about room temperature may be provided.
  • the print target base material 22 is not particularly limited, and examples thereof include paper, film, metal, and composite materials of these.
  • the print target base material 22 may have a sheet shape. It may be one-side printable or both-side printable.
  • ultraviolet irradiation by the light sources 24a, 24b, and 24c may be weakened or skipped, and ultraviolet irradiation may be performed with the light source 24d after a plurality of colors are printed. This allows for energy saving and cost saving.
  • Examples of a printed matter recorded with the ink of the present invention include not only ones that are printed over a smooth surface such as regular paper and resin film, but also ones that are printed over a print target surface having undulations, and ones that are printed over a print target surface made of various materials such as metal and ceramic.
  • the photopolymerizable compound and a photocurable composition of the present invention are suitable as a material of an ink, but can also be used for a molding resin, a paint, an adhesive, an insulating material, a release agent, a coating material, a sealing material, various types of resists, and various types of optical materials.
  • the photocurable composition of the present invention can be used as a three-dimensional object formation material, and, for example, can be used as a binder of powder particles used in a powder layer stacking method, which is one of three-dimensional object forming methods, or as a three-dimensional object formation material of a material jet method of forming a three-dimensional object by jetting a photocurable composition onto a predetermined region, curing it with an ultraviolet ray, and sequentially stacking up such cured products, or of an optical modeling method of forming a three-dimensional object by sequentially stacking up cured layers having a predetermined shape that are formed by emitting an ultraviolet ray to a storage pool of a photocurable composition.
  • a three-dimensional object forming apparatus for when the photocurable composition of the present invention is used as a three-dimensional object formation material is not particularly limited, and may be a publicly-known apparatus.
  • a compound 1 was synthesized according to the procedure below.
  • the yellow oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (200 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (1.8 g) of the compound 1 represented by the chemical formula below (yield: about 28%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 2 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (5.7 g) (25 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (3.6 g) (36 mmol) was added thereto. Then, after they were cooled to about - 10°C, acetic acid chloride (2.4 g) (30 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the yellow oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (200 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (3.2 g) of the compound 2 represented by the chemical formula below (yield: about 47%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 3 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (13.7 g) (60 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (150 mL), and after a flask was internally purged with an argon gas, triethyl amine (7.9 g) (78 mmol) was added thereto. Then, after they were cooled to about - 10°C, propionyl chloride (7.2 g) (78 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • a compound 4 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (11.4 g) (50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (7.6 g) (75 mmol) was added thereto. Then, after they were cooled to about - 10°C, butyryl chloride (6.9 g) (65 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the yellow oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (300 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (2.9 g) of the compound 4 represented by the chemical formula below (yield: about 19%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 5 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (9.1 g) (40 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (6.1 g) (60 mmol) was added thereto. Then, after they were cooled to about - 10°C, pivaloyl chloride (6.0 g) (50 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, then they were stirred at room temperature for 2 hours, and then stirred at from 35°C to 40°C for 3 hours.
  • the yellow oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (300 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (2.0 g) of the compound 5 represented by the chemical formula below (yield: about 16%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 6 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (6.9 g) (30 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (4.9 g) (48 mmol) was added thereto. Then, after they were cooled to about - 10°C, 2-ethyl hexanoyl chloride (6.5 g) (40 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the colorless oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (300 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (3.5 g) of the compound 6 represented by the chemical formula below (yield: about 33%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • hexane and ethyl acetate were used as eluates
  • a compound 7 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (6.9 g) (30 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (4.9 g) (48 mmol) was added thereto. Then, after they were cooled to about - 10°C, lauroyl chloride (dodecanoyl chloride) (8.8 g) (40 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the colorless oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (300 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (1.5 g) of the compound 7 represented by the chemical formula below (yield: about 12%).
  • a compound 8 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (13.7 g) (60 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (150 mL), and after a flask was internally purged with an argon gas, triethyl amine (7.9 g) (78 mmol) was added thereto. Then, after they were cooled to about - 10°C, methyl chloroformate (7.4 g) (78 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the pale pink oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (390 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (2.3 g) of the compound 8 represented by the chemical formula below (yield: about 13%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 9 was synthesized according to the procedure below.
  • Glycerol dimethacrylate (13.7 g) (60 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (150 mL), and after a flask was internally purged with an argon gas, triethyl amine (7.9 g) (78 mmol) was added thereto. Then, after they were cooled to about - 10°C, methyl chloroformate (8.5 g) (78 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the pale pink oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (380 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a brown oily matter (5.2 g) of the compound 9 represented by the chemical formula below (yield: about 29%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • a compound 10 was synthesized according to the procedure below.
  • 3-methylpentane-1,3,5-triol (6.7 g) (50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (12.1 g) (120 mmol) was added thereto. Then, after they were cooled to about - 10°C, methacrylic acid chloride (10.5 g) (100 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • the brown oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (350 g) and hexane and ethyl acetate were used as eluates, to thereby obtain a pale yellow oily matter (8.9 g) of the compound 10 represented by the chemical formula below (yield: about 66%).
  • WAKOGEL C300 manufactured by Wako Pure Chemical Industries, Ltd.
  • hexane and ethyl acetate were used as eluates
  • a compound 11 was synthesized according to the procedure below.
  • 3-methylpentane-1,3,5-triol (13.4 g) (100 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was added to dehydrated dichloromethane (100 mL), and after a flask was internally purged with an argon gas, triethyl amine (24.3 g) (240 mmol) was added thereto. Then, after they were cooled to about - 10°C, acrylic acid chloride (21.7 g) (240 mmol) was dropped thereto slowly such that the internal temperature of the system would be from -10°C to -5°C, and then they were stirred at room temperature for 2 hours.
  • a comparative compound 1 was synthesized according to the procedure below.
  • a deposited product was removed by filtration, and the filtrate was washed with water, a saturated sodium bicarbonate aqueous solution, and a saturated sodium chloride aqueous solution, dried with sodium sulfate, and then concentrated at reduced pressure, to thereby obtain a brown oily matter.
  • the obtained oily matter was refined by column chromatography (WAKOGEL C300, 250g), to thereby obtain a colorless oily matter (7.8g) of the comparative compound 1 represented by the chemical formula below (yield: about 68%).
  • a comparative compound 2 was synthesized according to the procedure below.
  • a deposited product was removed by filtration, and the filtrate was washed with water, a saturated sodium bicarbonate aqueous solution, and a saturated sodium chloride aqueous solution, dried with sodium sulfate, and then concentrated at reduced pressure, to thereby obtain a brown oily matter.
  • the obtained oily matter was refined by column chromatography (WAKOGEL C300, 250g), to thereby obtain a colorless oily matter (10.4 g) of the comparative compound 2 represented by the chemical formula below (yield: about 80%).
  • a comparative compound 3 was synthesized according to the procedure below.
  • DL-tartaric acid (7.5 g) (50 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in methanol (200 mL), HfCl 4 (THF) 2 (0.46 g) (1 mmol) was added thereto, and they were stirred at room temperature for 24 hours.
  • the reaction mixture was filtered to remove insoluble matters, and the filtrate was concentrated at reduced pressure to thereby obtain a colorless oily matter (8.8 g) represented by the chemical formula below as an intermediate product (yield: about 99%).
  • the reddish brown oily matter was refined by column chromatography in which the column was filled with WAKOGEL C300 (manufactured by Wako Pure Chemical Industries, Ltd.) (250g) and hexane and ethyl acetate were used as eluates, to thereby obtain a colorless oily matter (3.5 g) of the comparative compound 3 represented by the chemical formula below (yield: about 55%).
  • Photopolymerizability of each photocurable composition was evaluated with a measuring instrument composed of DSC-7020 (manufactured by SII Inc.) and a spot light source LA-410UV (manufactured by Hayashi Watch-Works Co., Ltd.).
  • an exothermic amount of the photopolymerizable compound when it was irradiated with an ultraviolet ray having a wavelength of 365 nm at 200 mW/cm 2 for a period of time enough for the photopolymerizable compound to complete the polymerization was measured twice for each sample.
  • the exothermic amount obtained by the first measurement included an exothermic amount due to the ultraviolet irradiation, in addition to an exothermic amount due to the polymerization of the photopolymerizable compound.
  • the sample that had completed the polymerization at the first measurement was irradiated with an ultraviolet ray again under the same conditions to measure an exothermic amount excluding an exothermic amount due to polymerization of the photopolymerizable compound.
  • an exothermic amount due to the polymerization of the photopolymerizable compound was calculated based on the difference between the first and second exothermic amounts.
  • a time T1 [s] taken from when the ultraviolet irradiation was started until when the maximum exothermic amount was reached was used as an index for comparison of the photopolymerization speed.
  • Photo-curability of each photocurable composition was measured with a measuring instrument composed of VAR200AD (manufactured by Reologica Instruments, Inc.) and an LED light source LIGHTNINGCURE LC-L1 (manufactured by Hamamatsu Photonics K.K.). Specifically, a sample was inserted in a gap of 10 ⁇ m between cone and plate having a diameter of 20 mm, and then irradiated with an ultraviolet ray having a wavelength of 365 nm at 50 mW/cm 2 , to measure changes of viscoelasticity until elastic modulus reached a saturated level. The maximum value of elastic modulus was determined from the measurement result and used as an indicator of a cured level.
  • VAR200AD manufactured by Reologica Instruments, Inc.
  • LIGHTNINGCURE LC-L1 manufactured by Hamamatsu Photonics K.K.
  • an elastic modulus of 1 ⁇ 10 4 Pa indicates a sufficiently cured level.
  • the photocurable compositions of all Examples and Comparative Examples had an elastic modulus of 1 ⁇ 10 5 Pa. This was because their elastic modulus was saturated substantially at 1 ⁇ 10 5 Pa, and elastic modulus measurement beyond that level was impossible. The result showed that all of the samples could form a hard state by being irradiated with sufficient light (by being given a lot of light energy). A sample of which elastic modulus reaches 1 ⁇ 10 5 Pa by a shorter period of time of light irradiation can be cured with lower energy and has a better photo-curability.
  • T1 which is the indicator of photopolymerizability
  • T2 indicates a better photopolymerizability as the value is smaller, and is preferably 7 seconds or shorter, and more preferably 5 seconds or shorter.
  • the curing energy which is the indicator of photo-curability, likewise indicates a better photo-curability as the value is smaller, and is preferably 350 mJ/cm 2 or less, and more preferably 250 mJ/cm 2 or less.
  • the photopolymerizable compounds of the present invention achieved the effects described above because they had a plurality of polymerizable functional groups and a specific polar structure in a molecule thereof. Among them, photopolymerizable compounds having a group having an ester structure had little odor, were excellent in photopolymerizability and photo-curability, and had a particularly low viscosity, as can be seen.
  • the photopolymerizable compounds of Comparative Examples 4a and 5a were bifunctional methacrylate compounds having an ethylene glycol chain on their mother nucleus structure.
  • Comparative Example 4a having a shorter ethylene glycol chain had a lower viscosity, but the photocurable composition of Comparative Example 4b using the same had poor achievements in both of photopolymerizability and photo-curability.
  • Comparative Example 5a having a longer ethylene glycol chain had a bit higher viscosity, but the corresponding photocurable composition achieved a higher photo-curability owing to the influence of the higher molecular weight of the monomer.
  • it can be seen that its photoreactivity was low (T1 9.0 s). This means that the reactive sites of the monomer tend to remain unchanged in the photo-curing process.
  • the photopolymerizable compounds of Comparative Examples 6a and 7a into which a secondary hydroxyl group, which was a protic polar structure, was incorporated, and the photopolymerizable compound of Comparative Example 8a into which a urethane structure was incorporated had little odor, and the photocurable compositions of Comparative Examples 6b to 8b using the same achieved better photopolymerizability and photo-curability than the photocurable compositions of Comparative Examples 1b to 5b.
  • the inks of Examples 1c to 11c and Examples 1d to 11d were each ink-jetted onto a glass slide, and then irradiated and cured with an ultraviolet ray having a wavelength of 365 nm at 200 mW/cm 2 with a UV irradiator LH6 (manufactured by Fusion Systems Japan Co., Ltd.). As a result, the inks could be ink-jetted without troubles, and the respective ink images cured sufficiently.
  • the inks substantially correspond to products composed of the photocurable compositions of Examples 1b to 11b. However, just to make sure, photopolymerizability and photo-curability of the inks were measured in the same manner as for the photocurable compositions. As a result, it was confirmed that the inks were excellent just the same as the photocurable compositions.
  • the pen tip of a dip pen was dipped in the inks of Examples 1c to 11c and Examples 1d to 11d, and characters were written on a PET film and regular paper.
  • the written inks were irradiated and cured with an ultraviolet ray having a wavelength of 365 nm at 200 mW/cm 2 with a UV irradiator LH6 (manufactured by Fusion Systems Japan Co., Ltd.).
  • an ultraviolet ray having a wavelength of 365 nm at 200 mW/cm 2 with a UV irradiator LH6 (manufactured by Fusion Systems Japan Co., Ltd.).

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EP15807470.8A 2014-06-10 2015-05-19 Ink, ink cartridge, inkjet recording apparatus, printed matter, photopolymerizable compound, photocurable composition, three-dimensional object formation material, and three-dimensional object Active EP3155056B1 (en)

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US9718218B2 (en) 2012-03-13 2017-08-01 Structured Polymers, Inc. Materials for powder-based additive manufacturing processes
JP6759577B2 (ja) * 2015-02-24 2020-09-23 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、加飾体、及び活性エネルギー線重合性化合物
CN108699254B (zh) 2015-12-22 2021-04-20 赢创运营有限公司 用于生产可消耗性粉末的系统和方法
WO2018038954A1 (en) 2016-08-25 2018-03-01 3M Innovative Properties Company Coloured curable composition for additive manufacturing processes, 3-dim composite article and use thereof
JP6759993B2 (ja) * 2016-11-09 2020-09-23 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク、収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、加飾体、及び活性エネルギー線重合性化合物
JP6844226B2 (ja) * 2016-11-30 2021-03-17 株式会社リコー 光重合性インクジェットインク、印刷塗工方法、印刷塗工物、組成物収容容器、及び印刷塗工装置
US10858527B2 (en) 2017-07-19 2020-12-08 Ricoh Company, Ltd. Composition, cured product, image forming apparatus, and image forming method
JP7102992B2 (ja) 2017-09-29 2022-07-20 株式会社リコー 組成物、収容容器、像形成装置、及び像形成方法
US10822507B2 (en) 2018-03-13 2020-11-03 Ricoh Company, Ltd. Curable composition, curable ink, composition stored container, image forming apparatus, image forming method, cured product, and decorated body
JP7024532B2 (ja) 2018-03-19 2022-02-24 株式会社リコー 組成物、硬化物、収容容器、像形成装置、及び像形成方法
US11059985B2 (en) 2018-07-30 2021-07-13 Ricoh Company, Ltd. Composition, cured product, storage container, image forming apparatus, and image forming method
US11208516B2 (en) 2018-07-30 2021-12-28 Ricoh Company, Ltd. Composition, cured product, storage container, image forming apparatus, and image forming method
US11084940B2 (en) 2018-07-30 2021-08-10 Ricoh Company, Ltd. Composition, cured product, storage container, image forming apparatus, and image forming method
US11529302B2 (en) 2018-07-31 2022-12-20 Ricoh Company, Ltd. Composition, artificial nail composition, nail decoration material, artificial nail, stored container, image forming apparatus, and image forming method
US11096883B2 (en) 2018-07-31 2021-08-24 Ricoh Company, Ltd. Composition, artificial nail composition, nail decoration material, artificial nail, stored container, image forming apparatus, and image forming method
KR102664924B1 (ko) 2019-02-11 2024-05-14 삼성디스플레이 주식회사 발광 소자 용매, 이를 포함하는 발광 소자 잉크 및 표시 장치의 제조 방법
US11920045B2 (en) 2019-04-01 2024-03-05 Ricoh Company, Ltd. Active-energy-ray-curable composition, active-energy-ray-curable ink composition, active-energy-ray-curable inkjet ink composition, composition stored container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured material, and decorated article
JP2021031669A (ja) * 2019-08-28 2021-03-01 東京応化工業株式会社 硬化性インク組成物、硬化物、及びナノコンポジット
JP7335975B2 (ja) * 2019-11-28 2023-08-30 東京応化工業株式会社 感光性インク組成物、硬化物、ディスプレイパネル、及び硬化物の製造方法
KR20220107247A (ko) * 2019-11-28 2022-08-02 도쿄 오카 고교 가부시키가이샤 감광성 잉크 조성물, 경화물, 디스플레이 패널, 및 경화물의 제조 방법
JP6876282B1 (ja) 2020-05-14 2021-05-26 株式会社リコー （メタ）アクリル酸アミド化合物の製造方法
CN113043762A (zh) * 2021-02-04 2021-06-29 宿州市博彩印刷有限公司 一种薄本印刷工艺

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6011051B2 (ja) * 1980-06-30 1985-03-22 大日本インキ化学工業株式会社 光硬化性組成物
JPH0672955B2 (ja) * 1984-02-27 1994-09-14 株式会社日立製作所 粉体廃棄物の固化方法
JPS62265318A (ja) * 1986-05-13 1987-11-18 Kyowa Gas Chem Ind Co Ltd 嫌気硬化性組成物
JP3622206B2 (ja) 1992-05-21 2005-02-23 大日本インキ化学工業株式会社 側鎖型重合性化合物及びそれを用いた液晶デバイス
JP3648636B2 (ja) * 1992-08-27 2005-05-18 大日本インキ化学工業株式会社 活性エネルギー線硬化樹脂用反応性希釈剤及びその製造法
DE19544673C2 (de) 1995-11-30 2001-03-29 Heraeus Kulzer Gmbh & Co Kg Dentaladhäsive
JP2003021900A (ja) * 2001-07-06 2003-01-24 Toagosei Co Ltd エッチングレジスト用硬化型組成物
JP2003246818A (ja) 2002-02-25 2003-09-05 Konica Corp 活性エネルギー線硬化型組成物、それを用いた活性エネルギー線硬化型インクジェット記録用インクおよび平版印刷版
JP2005165246A (ja) * 2003-12-04 2005-06-23 Yasuhara Chemical Co Ltd 感光性組成物
JP4611648B2 (ja) 2004-02-26 2011-01-12 セーレン株式会社 紫外線硬化型インク原液およびそれを用いた紫外線硬化型インクジェットインクの製造方法
US8946320B2 (en) * 2004-03-22 2015-02-03 Hewlett-Packard Development Company, L.P. Ink system containing polymer binders
AU2006226818B2 (en) * 2005-03-24 2011-05-12 Medtronic, Inc. Modification of thermoplastic polymers
JP5213395B2 (ja) 2007-09-14 2013-06-19 富士フイルム株式会社 インクジェット記録用インク組成物、及び、インクジェット記録方法
JP5692495B2 (ja) 2010-03-19 2015-04-01 セイコーエプソン株式会社 インクジェット記録用放射線硬化型インク組成物、ならびにインクジェット記録方法
JP5789879B2 (ja) 2011-03-17 2015-10-07 株式会社リコー インクジェット記録用インク組成物
JP5803583B2 (ja) 2011-11-07 2015-11-04 株式会社リコー 光重合性インクジェットインク
US9212132B2 (en) * 2011-12-05 2015-12-15 Ricoh Company Ltd. (Meth)acrylic acid ester, activation energy ray curing composition, and inkjet recording ink
JP2013147462A (ja) * 2012-01-20 2013-08-01 Toyo Ink Sc Holdings Co Ltd 反応性化合物、およびそれを用いた重合性組成物、およびそれを用いた活性エネルギー線硬化型インクジェットインキ
JP5929313B2 (ja) 2012-02-29 2016-06-01 東洋インキＳｃホールディングス株式会社 重合性組成物、およびそれを用いた活性エネルギー線硬化型インクジェットインキ
JP5803746B2 (ja) 2012-03-02 2015-11-04 株式会社リコー 光重合性インクジェットインク、インクカートリッジ
JP6226174B2 (ja) 2012-10-26 2017-11-08 株式会社リコー インク、インクカートリッジ、インクジェット記録装置、記録物、重合性化合物及び組成物
JP6277806B2 (ja) 2013-06-05 2018-02-14 株式会社リコー インク
EP3061795B1 (en) 2015-02-24 2019-04-24 Ricoh Company, Ltd. Active-energy-ray-curable composition, active-energy-ray-curable ink, composition stored container, two-dimensional or three-dimensional image forming apparatus, method for forming two-dimensional or three-dimensional image, cured material, decorative body, and active energy ray polymerizable compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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CN106459627B (zh) 2019-10-11
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